Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized. The organometallic Au(I) complexes obtained show fluorescence in the solution and dual singlet-triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene-terpyridine part with no Au(I) involved. In addition, a study of the nature of the excited states for the "dimer" with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au(I)-containing organometallic aggregation-induced-emission luminogens.

Keep it tight: a crucial role of bridging phosphine ligands in the design and optical properties of multinuclear coinage metal complexes.

Copper subgroup metal ions in the +1 oxidation state are classical candidates for aggregation via non-covalent metal-metal interactions, which are supported by a number of bridging ligands. The bridging phosphines, soft donors with a relatively labile coordination to coinage metals, serve as convenient and essential components of the ligand environment that allow for efficient self-assembly of discrete polynuclear aggregates. Simultaneously, accessible and rich modification of the organic spacer of such P-donors has been used to generate many fascinating structures with attractive photoluminescent behavior. In this work we consider the development of di- and polynuclear complexes of M(i) (M = Cu, Ag, Au) and their photophysical properties, focusing on the effect of phosphine bridging ligands, their flexibility and denticity.

Hexavanadate-Organogold(I) Hybrid Compounds: Synthesis by the Azide-Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution.

The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a transoid fashion (n-Bu4N)2[V6O13{(OCH2)3CCH2(N3C2C6H5)AuP(C6H4OMe)3}2] (POMNAu) and (n-Bu4N)2[V6O13{(OCH2)3CCH2OCH2(C2N3H)AuP(C6H4OMe)3}2] (POMCAu) have been prepared by azide-alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.

Luminescence behaviour of Au(I)-Cu(I) heterobimetallic coordination polymers based on alkynyl-tris(2-pyridyl)phosphine Au(I) complexes.

A set of alkynyl-tris(2-pyridyl)phosphine Au(i) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely 'scorpionate' PPy3 and the C[triple bond, length as m-dash]C bond, allowed these ditopic metalloligands to be selectively linked to 1D coordination polymers by reaction with Cu(i), which used both Cu-(N-PPy3) and Cu-(η2-C[triple bond, length as m-dash]C) coordination modes. Single-crystal and powder XRD, NMR, and XPS techniques were used to characterize the coordination polymers obtained. Heterobimetallic Au(i)-Cu(i) coordination polymers demonstrate triplet photoluminescence which was studied by spectroscopic and computational methods to understand the pathway of energy transfer inside the chain of linked chromophore centres. The intriguing feature of the electronic structure of heterobimetallic supramolecular assemblies is the 'long-distance' electronic transition involving PhC2 and PPy3 ligands located at a distance of more than 1 nm from each other. Thus, the assembly of a heterobimetallic coordination polymer from relatively simple 'building blocks' retains the block-wise nature of the electronic structure, but the photophysical properties of the polymer are fundamentally different from the properties of discrete organometallic components.